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Six members of the 1,ω-bis(4-cyanobiphenyl-4′-yl) alkanes are reported and referred to as CBnCB in which n = 1, 15, 16, 17, 19 and 20 and indicates the number of methylene units in the spacer separating the two cyanobiphenyl units. The behaviour of CB3CB is revisited. The temperature dependence of the refractive indices, optical birefringence, and dielectric permittivities measured in the nematic, N, phase for selected homologues are reported. The dimers with n ≥ 15 showed an enantiotropic N phase, and for the odd members the twist-bend nematic, NTB, phase was observed. CB3CB shows a direct NTB-isotropic, I, transition whereas for CB1CB a virtual NTB-I transition is found. The temperature dependence of the bend elastic constant, K33, measured in the oblique helicoidal cholesteric state formed by mixtures of CBnCB with a chiral additive S811, shows strong non-monotonous behaviour with a deep minimum near the transition point to the NTB phase. The minimum value of K_33 decreases as n increases. The long even members of the CBnCB series show similar values of TNI to their odd-membered counterparts but their estimated values of TNTBN are considerably lower. This is attributed to molecular shape and its effect on K33.more » « less
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A unique morphology for bent-core liquid crystals forming the B4 phase has been found for a class of tris-biphenyl bent-core liquid crystal molecules with a single chiral side chain in the longer para -side of the molecule. Unlike the parent molecules with two chiral side chains or a chiral side chain in the shorter meta -side, which form helical nano- or microfilament B4 phases, the two derivatives described here form heliconical-layered nanocylinders composed of up to 10 coaxial heliconical layers, which can split or merge, braid, and self-assemble into a variety of modes including feather- or herringbone-type structures, concentric rings, or hollow nest-like superstructures. These multi-level hierarchical self-assembled structures, rivaling muscle fibers, display blue structural color and show immense structural and morphological complexity.more » « less
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The effect of the molecular chirality of chiral additives on the nanostructure of the twist-bend nematic (N TB ) liquid crystal phase with ambidextrous chirality and nanoscale pitch due to spontaneous symmetry breaking is studied. It is found that the ambidextrous nanoscale pitch of the N TB phase increases by 50% due to 3% chiral additive, and the chiral transfer among the biphenyl groups disappears in the N TB * phase. Most significantly, a twist-grain boundary (TGB) type phase is found at c > 1.5 wt% chiral additive concentrations below the usual N* phase and above the non-CD active N TB * phase. In such a TGB type phase, the adjacent blocks of pseudo-layers of the nanoscale pitch rotate across the grain boundaries.more » « less
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Abstract The range of possible morphologies for bent‐core B4 phase liquid crystals has recently expanded from helical nanofilaments (HNFs) and modulated HNFs to dual modulated HNFs, helical microfilaments, and heliconical‐layered nanocylinders. These new morphologies are observed when one or both aliphatic side chains contain a chiral center. Here, the following questions are addressed: which of these two chiral centers controls the handedness (helicity) and which morphology of the nanofilaments is formed by bent‐core liquid crystals with tris‐biphenyl diester core flanked by two chiral 2‐octyloxy side chains? The combined results reveal that the longer arm of these nonsymmetric bent‐core liquid crystals controls the handedness of the resulting dual modulated HNFs. These derivatives with opposite configuration of the two chiral side chains now feature twice as large dimensions compared to the homochiral derivatives with identical configuration. These results are supported by density functional theory calculations and stochastic dynamic atomistic simulations, which reveal that the relative difference between thepara‐ andmeta‐sides of the described series of compounds drives the variation in morphology. Finally, X‐ray diffraction, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and atomic force microscopy (AFM) data also uncover the new morphology for B4 phases featuringp2/msymmetry within the filaments and less pronounced crystalline character.more » « less
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